The present invention relates to a polyarylene, a teraryl and a teraryl precursor, as well as to a method for producing a polyarylene. More particularly, the invention relates to a polyarylene having terarylene recurring units on the backbone and a method for production thereof.
Polyarylenes are of interest because the arylene group as a recurring unit has excellent thermal and chemical stability. Also, polyarylenes have been attracting considerable attention to their peculiar physical properties because of the advanced xcfx80-electron conjugated system.
A variety of applications as, e.g., conductive polymers are anticipated for polyarylenes. Polyphenylene s may also be either oxidized or reduced so that anions or cations are doped to form p type or n type semiconductors. Utilizing the property, it is also expected to apply poly(p-phenylene) to electrode materials or apply as display elements using a change in absorbance upon oxidation or reduction.
Moreover, polyarylenes are expected to be applicable to macro molecule light emitting elements. In this field, elements called macro molecule light emitting electrochemical elements (LEC) have been proposed lately and drawn attention in view of their high luminous efficiency. The structure includes two electrodes, between which a electrically conductive polymer material and a polymer membrane comprising polyethylene oxide having ionic conductivity and a substrate salt are inserted. It is assumed that the principle of working mechanism is based on the input of positive and negative charges from the electrodes and the transfer of both positive and negative ions of the substrate salt as a dopant, whereby a p-n junction would be formed in the membrane. If an ionic conductivity is further imparted to conductive polymer substances having an electronic conductivity, such light emitting elements will be manufactured using a sole material, not with the composite membrane mentioned above, resulting in a great advantage in manufacturing steps.
Processes for manufacturing polyarylenes such as polyphenylene have been hitherto limited. For manufacturing polyphenylenes, for example, oxidative cation polymerization called the Kovacic process, which is polycondensation using benzene as a monomer, is known. As is described in P. Kovacic, et al., Chem. Rev., 1987, 87, 357-379, an oxidizing agent such as cupric chloride and a Lewis acid catalyst such as aluminum chloride are employed to form insoluble polyphenylene of uncertain structure. It is reported that polyphenylene formed by oxidation of benzene is branched polyphenylene with a low molecular weight.
Further processes are proposed for manufacturing polyarylenes, which include electrochemical oxidative polymerization (a process using a cupric chloride-lithium aluminum hexafluoride-based electrolyte and applying a voltage between electrodes to produce a polymer on the electrodes); as polycondensation of substituted benzene derivatives, Wurtz-Fittig reaction (a process involving condensation of a dihalogenobenzene with an alkali metal) Ullmann reaction (a process involving condensation of diiodobenzene with a metal copper), Grignard reaction called Yamamoto method (a process involving condensation of a dihalogenobenzene Grignard derivative with a nickel chloride-bipyridyl complex), diazonium coupling (a process involving condensation of a diazonium derivative with sodium nitrite/hydrochloric acid followed by treatment with copper chloride); as processes via precursors, dehydration of cyclohexadiene polymer, a bio-engineering method (which comprises oxidizing benzene with bacteria to synthesize 5,6-dihydroxycyclohexane-1,3-diene, subjecting the carbonic acid ester of the diene to radical polymerization and then heating the resulting intermediate polymer to effect synthesis); and so on.
However, polyarylenes having terarylene recurring units are extremely rarely known. In these polyarylenes, it has been sought to introduce substituents freely into the central arylene of the terarylene unit and modify the terarylene in various ways.
For example, Japanese Patent Unexamined Publication (Laid-open) No. 9-309945 discloses polyphenylene copolymers. According to this patent publication, polyphenylene copolymers are synthesized using various types of monoarylenes as recurring units.
Now, an object of the present invention is to provide polyarylenes containing a terarylene as the recurring unit.
In a first aspect of the present invention, there are provided polyarylenes comprising a recurring unit represented by formula (I) or (II) below: 
(wherein:
Ar1 and Ar2 which may be the same or different, each represents independently an arylene having 4 to 18 carbon atoms, which may be substituted and may contain 1 to 5 nitrogen atoms;
R1 and R2, which may be the same or different, each represents independently a C1-C20 hydrocarbon group which may optionally be substituted, a C1-C20 alkoxy group which may optionally be substituted, a C6-C20 aryloxy group which may optionally be substituted, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5) (wherein R3, R4 and R5, which may be the same or different, each represents independently a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group)
provided that, in the recurring unit of formula (I), R1 and R2 may form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may be substituted;
A1 and A2, which may be the same or different, each represents hydrogen atom; a C1-C20 hydrocarbon group which may optionally be substituted; a C1-C20 alkoxy group which may optionally be substituted; a C6-C20 aryloxy group which may optionally be substituted; a C6-C20 alkylaryloxy group which may optionally be substituted; a C1-C20 alkoxycarbonyl group which may optionally be substituted; a C6-C20 aryloxycarbonyl group which may optionally be substituted; cyano group (xe2x80x94CN); carbamoyl group (xe2x80x94C(xe2x95x90O)NH2); a haloformyl group (xe2x80x94C(xe2x95x90O)xe2x80x94X, wherein X is a halogen atom); or formyl group (xe2x80x94C(xe2x95x90O)xe2x80x94H); and,
n is an integer of 2 or more).
In the present invention, preferably, A1 and A2, which may be the same or different, each represents independently a phenylene group which may optionally be substituted.
Also, the recurring unit is preferably a recurring unit shown by formula (I) described above, wherein R1 and R2 may form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may optionally be substituted.
Furthermore, the C1-C20 hydrocarbon group is preferably a linear or branched C1-C20 alkyl group, a linear or branched C2-C20 alkenyl group, a linear or branched C2-C20 alkynyl group, a linear or branched C3-C20 allyl group, a linear or branched C4-C20 alkadienyl group, a linear or branched C4-C20 polyenyl group, a C6-C18 aryl group, a C6-C20 alkylaryl group, a C6-C20 arylalkyl group, a C4-C20 cycloalkyl group, or a C4-C20 cycloalkenyl group.
In a further aspect of the invention, there is provided a polyarylene comprising a recurring unit represented by the formula (I) below: 
(wherein:
Ar1 and Ar2, which may be the same or different, each represents independently a paraarylene having 4 to 18 carbon atoms, which may be substituted and may contain 1 to 5 nitrogen atoms;
R1 and R2, which may be the same or different, each represents independently a C1-C20 hydrocarbon group which may be substituted, a C1-C20 alkoxy group which may be substituted, a C6-C20 aryloxy group which may be substituted, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5) (wherein R3, R4 and R5, which may be the same or different, each represents independently a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group);
provided that, in the recurring unit of formula (I), R1 and R2 may form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may be substituted;
A1 and A2, which may be the same or different, each represents independently hydrogen atom; a C1-C20 hydrocarbon group which may be substituted; a C1-C20 alkoxy group which may be substituted; a C6-C20 aryloxy group which may be substituted; a C6-C20 alkylaryloxy group which may be substituted; an alkoxycarbonyl group which may be substituted; a C6-C20 aryloxycarbonyl group which may be substituted; cyano group (xe2x80x94CN); carbamoyl group (xe2x80x94C(xe2x95x90O)NH2); a haloformyl group (xe2x80x94C(xe2x95x90O)xe2x80x94X, wherein X is a halogen atom); or formyl group (xe2x80x94C(xe2x95x90O)xe2x80x94H); and,
n is an integer of 2 or more).
In the present invention, preferably, A1 and A2, which may be the same or different, each represents independently a paraphenylene group which may optionally be substituted.
Also, the recurring unit is preferably a recurring unit shown by formula (I) described above, wherein R1 and R2 form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may be substituted.
Furthermore, the C1-C20 hydrocarbon group is preferably a linear or branched C1-C20 alkyl group, a linear or branched C2-C20 alkenyl group, a linear or branched C2-C20 alkynyl group, a linear or branched C3-C20 allyl group, a linear or branched C4-C20 alkadienyl group, a linear or branched C4-C20 polyenyl group, a C6-C18 aryl group, a C6-C20 alkylaryl group, a C6-C20 arylalkyl group, a C4-C20 cycloalkyl group, or a C4-C20 cycloalkenyl group.
In a further aspect of the invention, there is provided a resin composition comprising the polyarylene described above and a synthetic organic polymer.
In a further aspect of the invention, there is provided a teraryl shown by formula (III) or (IV) below: 
(wherein
Ar1 and Ar2, which may be the same or different, each represents independently an arylene having 4 to 18 carbon atoms, which may be substituted and may contain 1 to 5 nitrogen atoms;
R1 and R2, which may be the same or different, each represents independently a C1-C20 hydrocarbon group which may optionally be substituted, a C1-C20 alkoxy group which may optionally be substituted, a C6-C20 aryloxy group which may optionally be substituted, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5) (wherein R3, R4 and R5, which may be the same or different, each represents independently a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group)
provided that, in the recurring unit of formula (III), R1 and R2 may form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may optionally be substituted;
A1 and A2, which may be the same or different, each represents independently hydrogen atom; a C1-C20 hydrocarbon group which may optionally be substituted; a C1-C20 alkoxy group which may optionally be substituted; a C6-C20 aryloxy group which may optionally be substituted; a C6-C20 alkylaryloxy group which may optionally be substituted; a C1-C20 alkoxycarbonyl group which may optionally be substituted; a C6-C20 aryloxycarbonyl group which may optionally be substituted; cyano group (xe2x80x94CN); carbamoyl group (xe2x80x94C(xe2x95x90O)NH2); a haloformyl group (xe2x80x94C(xe2x95x90O)xe2x80x94X, wherein X is a halogen atom); or formyl group (xe2x80x94C(xe2x95x90O)xe2x80x94H); and,
X1 and X2, which may be the same or different, each represents independently a leaving group).
In a still further aspect of the present invention, there is provided a process for producing a polyarylene of formula (I) or (II) below: 
(wherein:
Ar1 and Ar2, which may be the same or different, each represents independently an arylene having 4 to 18 carbon atoms, which may be substituted and may contain 1 to 5 nitrogen atoms;
R1 and R2, which may be the same or different, each represents independently a C1-C20 hydrocarbon group which may optionally be substituted, a C1-C20 alkoxy group which may optionally be substituted, a C6-C20 aryloxy group which may optionally be substituted, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5) (wherein R3, R4 and R5, which may be the same or different, each represents independently a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group);
provided that, in the recurring unit of formula (I), R1 and R2 may form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may be substituted;
A1 and A2, which may be the same or different, each represents independently hydrogen atom; a C1-C20 hydrocarbon group which may optionally be substituted; a C1-C20 alkoxy group which may optionally be substituted; a C6-C20 aryloxy group which may optionally be substituted; a C6-C20 alkylaryloxy group which may optionally be substituted; a C1-C20 alkoxycarbonyl group which may optionally be substituted; a C6-C20 aryloxycarbonyl group which may optionally be substituted; cyano group (xe2x80x94CN); carbamoyl group (xe2x80x94C(xe2x95x90O)NH2); a haloformyl group (xe2x80x94C(xe2x95x90O)xe2x80x94X, wherein X is a halogen atom); or formyl group (xe2x80x94C(xe2x95x90O)xe2x80x94H); and,
n is an integer of 2 or more), which comprises polymerizing a teraryl represented by formula (III) or (IV) below: 
(wherein
Ar1, Ar2, R1, R2, A1 and A2 have the same significance as defined above; and,
X1 and X2, which may be the same or different, each represents independently a leaving group).
In a further aspect of the present invention, there is provided a process for producing a teraryl, which comprises reacting a metallacyclopentadiene represented by formula (V) or (VI) below: 
(wherein:
M is a metal from Groups III-V or the lanthanide series of the Periodic Table;
L1 and L2, which may be the same or different, each represents independently an anionic ligand, provided that L1 and L2 may be crosslinked;
Ar1 and Ar2, which may be the same or different, each represents independently an arylene having 4 to 18 carbon atoms, which may be substituted and may contain 1 to 5 nitrogen atoms;
R1 and R2, which may be the same or different, each represents independently a C1-C20 hydrocarbon group which may optionally be substituted, a C1-C20 alkoxy group which may optionally be substituted, a C6-C20 aryloxy group which may optionally be substituted, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5) (wherein R3, R4 and R5, which may be the same or different, each represents a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group).
provided that, in the metallacyclopentadiene shown by formula (V), R1 and R2 may form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may optionally be substituted; and,
X1 and X2, which may be the same or different, each represents independently a leaving group);
with an alkyne derivative represented by formula (VII) below:
A1axe2x80x94Cxe2x89xa1Cxe2x80x94A2axe2x80x83xe2x80x83(VII)
xe2x80x83(wherein;
A1a and A2a, which may be the same or different, each represents independently hydrogen atom; a C1-C20 hydrocarbon group which may optionally be substituted; a C1-C20 alkoxy group which may optionally be substituted; a C6-C20 aryloxy group which may optionally be substituted; a C6-C20 alkylaryloxy group which may optionally be substituted; a C1-C20 alkoxycarbonyl group which may optionally be substituted; a C6-C20 aryloxycarbonyl group which may optionally be substituted; a C6-C20 aryloxy group which may optionally be substituted; a C6-C20 alkylaryloxy group which may optionally be substituted; or cyano group (xe2x80x94CN);
to produce a teraryl represented by formula (IIIa) or (IVa) below: 
xe2x80x83(wherein each of Ar1, Ar2, R1, R2, A1a, A2a, X1 and X2 has the same significance as defined above).
In the present invention, preferably, M is a metal from Group IV or the lanthanide series of the Periodic Table; the anionic ligand is non-localized cyclic xcex75-coordination type ligand, a C1-C20 alkoxy group, a C6-C20 aryloxy group or a dialkylamide group.
The non-localized cyclic xcex75-coordination type ligand described above is preferably a cyclopentadienyl, indenyl, fluorenyl or azulenyl group, which may be substituted.
Furthermore, the reaction preferably proceeds in the presence of a compound containing a metal from Groups IX-XV of the Periodic Table.
In a still further aspect of the invention, there is provided a process for producing a polyarylene, which comprises reacting a metallacyclopentadiene represented by formula (V) or (VI) below: 
(wherein:
Ar1 and Ar2, which may be the same or different, each represents independently an arylene having 4 to 18 carbon atoms, which may be substituted and may contain 1 to 5 nitrogen atoms;
R1 and R2, which may be the same or different, each represents independently a C1-C20 hydrocarbon group which may be substituted, a C1-C20 alkoxy group which may be substituted, a C6-C20 aryloxy group which may be substituted, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5) (wherein R3, R4 and R5, which may be the same or different, each represents independently a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group);
provided that, in the metallacyclopentadiene shown by formula (V), R1 and R2 may form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may be substituted;
M is a metal from Groups III-V or the lanthanide series of the Periodic Table;
L1 and L2, which may be the same or different, each represents independently an anionic ligand, provided that L1 and L2 may be crosslinked; and,
X1 and X2, which may be the same or different, each represents independently a leaving group);
with an alkyne derivative represented by formula (VII) below:
A1axe2x80x94Cxe2x89xa1Cxe2x80x94A2axe2x80x83xe2x80x83(VII)
xe2x80x83(wherein;
A1a and A2a, which may be the same or different, each represents independently hydrogen atom; a C1-C20 hydrocarbon group which may be substituted; a C1-C20 alkoxy group which may be substituted; a C6-C20 aryloxy group which may be substituted; C6-C20 alkylaryloxy group which may be substituted; C1-C20 alkoxycarbonyl group which may be substituted; a C6-C20 aryloxycarbonyl group which may be substituted; or cyano group (xe2x80x94CN); to produce a teraryl represented by formula (IIIa) or (IVa) below: 
xe2x80x83(wherein each of Ar1, Ar2, R1, R2, A1a, A2a, X1 and X2 has the same significance as defined above); and polymerizing the resulting teraryl to produce the polyarylene represented by formula (Ia) or (IIa) below: 
xe2x80x83(wherein each of Ar1, Ar2, R1, R2, A1a and A2a has the same significance as defined above; and n is an integer of 2 or more).
In the present invention, preferably, M is a metal from Group IV or the lanthanide series of the Periodic Table; the anionic ligand is non-localized cyclic xcex75-coordination type ligand, a C1-C20 alkoxy group, a C6-C20 aryloxy group or a dialkylamide group.
The non-localized cyclic xcex75-coordination type ligand described above is preferably a cyclopentadienyl, indenyl, fluorenyl or azulenyl group, which may be substituted.
Furthermore, the reaction preferably proceeds in the presence of a compound containing a metal from Groups IX-XV of the Periodic Table.
In a still further aspect of the present invention, here is provided a metallacyclopentadiene represented by formula (V) or (VI) below: 
(wherein:
M is a metal from Groups III-V or the lanthanide series of the Periodic Table;
L1 and L2, which may be the same or different, each represents independently an anionic ligand, provided that L1 and L2 may be crosslinked;
Ar1 and Ar2, which may be the same or different, each represents independently an arylene having 4 to 18 carbon atoms, which may be substituted and may contain 1 to 5 nitrogen atoms;
R1 and R2, which may be the same or different, each represents independently a C1-C20 hydrocarbon group which may optionally be substituted, a C1-C20 alkoxy group which may optionally be substituted, a C6-C20 aryloxy group which may optionally be substituted, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5) (wherein R3, R4 and R5, which may be the same or different, each represents independently a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group);
provided that, in the metallacyclopentadiene shown by formula (V), R1 and R2 may form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may be substituted; and,
X1 and X2, which may be the same or different, each represents independently a leaving group).
In one aspect of the present invention, the polyarylenes represented by formula (I) or (II) described above are provided.
Ar1 and Ar2, which may be the same or different, each represents independently an arylene having 4 to 18 carbon atoms, which may be substituted and may contain 1 to 5 nitrogen atoms. Ar1 and Ar2 are preferably 5- to 18-membered, more preferably, 6- to 14-membered. Where the arylene contains nitrogen atoms, the number of nitrogen atoms is preferably 1 to 3, more preferably 1 or 2.
The arylene may be a carbon ring or may be a heterocyclic ring containing 1 to 5 nitrogen atoms. The arylene may be a monocyclic ring or a condensed ring. Examples of the arylene include phenylenes (1,3- and 1,4-phenylenes), 5-amino-1,3-phenylene, 4-benzoyl-1,3-phenylene, 5-benzoyl-1,3-phenylene, 2-benzoyl-1,4-phenylene, 4,4xe2x80x2-biphenyldiyl, 2-carboxy-methyl-1,4-phenylene, 4-carboxymethyl-1,3-phenylene, 5-carboxymethyl-1,3-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl, 5-phenoxy-1,3-phenylene, 2-phenyl-1,3-phenylene, 4-phenyl-1,3-phenylene, 5-phenyl-1,3-phenylene, 2-phenyl-1,4-phenylene, 2,6-pyridinediyl, 2,4-pyridinediyl, 3,5-pyridinediyl, 3,6-pyridinediyl, 5,8-quinolinediyl, 2,4-toluenediyl, 2,5-xylenediyl and so on. As isomers of the arylenes other than those at the 1,3- and 1,4-positions, which are not described above, there are, e.g., 2,4-quinolinediyl, 2,5-quinolinediyl, 2,6-quinolinediyl, and the like. Preferred examples of the arylenes are phenylene, naphthalenediyl and pyridinediyl, which may optionally be substituted, and more preferably, phenylene and naphthalenediyl which may optionally be substituted.
Examples of substituents on the arylenes shown by Ar1 and Ar2 are a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a C6-C20 aryloxy group, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5) (wherein R3, R4 and R5, which may be the same or different, each represents independently a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group)
The substituents on the arylenes are not limited to those given above, so long as they are substituents that can be introduced into the arylenes prior to or after the formation of a teraryl as the monomer, and unless they interfere with the reaction. Furthermore, by introducing an appropriate protecting group, various substituents can be introduced into the arylenes by publicly known reactions for ordinary aromatic compounds, for example, through nucleophilic substitution.
R1 and R2, which may be the same or different, each represents independently a C1-C20 hydrocarbon group which may optionally be substituted, a C1-C20 alkoxy group which may optionally be substituted, a C6-C20 aryloxy group which may optionally be substituted, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5 (wherein R3, R4 and R5, which may be the same or different, each represents independently a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group)
In the specification, the C1-C20 hydrocarbon group may be a saturated or unsaturated acyclic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon. Where the C1-C20 hydrocarbon group is acyclic, the group may be linear or branched. Examples of the C1-C20 hydrocarbon group include a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 allyl group, a C4-C20 alkadienyl group, a C4-C20 polyenyl group, a C6-C18 aryl group, a C6-C20 alkylaryl group, a C6-C20 arylalkyl group, a C4-C20 cycloalkyl group, and a C4-C20 cycloalkenyl group.
Examples of the alkyl group which is useful to practice the invention include, but are not limited to, methyl, ethyl, propyl, n-butyl, t-butyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, benzyl, 2-phenoxyethyl, etc.
Examples of the aryl group which is useful to practice the invention include, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, naphthyl, biphenyl, 4-phenoxyphenyl, 4-fluorophenyl, 3-carbomethoxyphenyl, 4-carbomethoxyphenyl, etc.
Examples of the alkoxy group which is useful to practice the invention include, but are not limited to, methoxy, ethoxy, 2-methoxyethoxy, t-butoxy, etc. Examples of the aryloxy group which is useful to practice the invention include, but are not limited to, phenoxy, naphthoxy, phenylphenoxy, 4-methylphenoxy, etc.
Examples of the amine group which is useful to practice the invention include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino, etc.
Examples of the group shown by formula: xe2x80x94Si(R3)(R4)(R5) include, but are not limited to, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethylsilyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl, etc.
Substitutents may be introduced into the C1-C20 hydrocarbon group, C1-C20 alkoxy group, and C6-C20 aryloxy group. Examples of the substituents are a halogen atom, hydroxy group, amino group, etc.
In the recurring unit shown by formula (I), however, R1 and R2 may form together a C4-C20 saturated or unsaturated ring which may be intervened by an oxygen atom and may be substituted. Preferably, The ring is a 4- to 16-membered ring, more preferably a 4- to 12-membered ring. The ring may optionally be substituted with substituents such as a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a C6-C20 aryloxy group, an amine group, hydroxy group or a group shown by formula: xe2x80x94Si(R3)(R4)(R5) (wherein R3, R4 and R5, which may be the same or different, each represents independently a C1-C20 alkyl group, a C6-C20 arylalkyl group, a C1-C20 alkoxy group or a C6-C20 arylalkyloxy group), etc.
A1 and A2, which may be the same or different, each represents independently hydrogen atom; a C1-C20 hydrocarbon group which may optionally be substituted; a C1-C20 alkoxy group which may optionally be substituted; a C6-C20 aryloxy group which may optionally be substituted; a C6-C20 alkylaryloxy group which may optionally be substituted; a C1-C20 alkoxycarbonyl group which may optionally be substituted; a C6-C20 aryloxycarbonyl group which may optionally be substituted; cyano group (xe2x80x94CN); carbamoyl group (xe2x80x94C(xe2x95x90O)NH2); a haloformyl group (xe2x80x94C(xe2x95x90O)xe2x80x94X, wherein X is a halogen atom); or formyl group (xe2x80x94C(xe2x95x90o)xe2x80x94H). The C1-C20 hydrocarbon group, the C1-C20 alkoxy group which may optionally be substituted, the C6-C20 aryloxy group which may optionally be substituted and the amino group are the same as those given for R1 and R2.
Examples of the alkoxycarbonyl group which is useful to practice the invention include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, 2-methoxyethoxycarbonyl, t-butoxycarbonyl, etc.
Examples of the aryloxycarbonyl group which is useful to practice the invention include, but are not limited to, phenoxycarbonyl, naphthoxycarbonyl, phenylphenoxycarbonyl, 4-methylphenoxycarbonyl, etc.
Carbamoyl group (xe2x80x94C(xe2x95x90O)NH2), the haloformyl group (xe2x80x94C(xe2x95x90O)xe2x80x94X, wherein X is a halogen atom), formyl group (xe2x80x94C(xe2x95x90O)xe2x80x94H) or the like can be mutually converted into cyano group or an alkoxycarbonyl group.
The polyarylenes of the present invention may also be copolymers. In addition to the terarylene recurring units described above, the polyarylenes may contain, e.g., one or more other recurring units. The other recurring unit may be an arylene. Examples of the arylene include phenylenes (1,3- and 1,4-phenylenes), 5-amino-1,3-phenylene, 4-benzoyl-1,3-phenylene, 5-benzoyl-1,3-phenylene, 2-benzoyl-1,4-phenylene, 4,4xe2x80x2-biphenyldiyl, 2-carboxy-methyl-1,4-phenylene, 4-carboxymethyl-1,3-phenylene, 5-carboxymethyl-1,3-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl, 5-phenoxy-1,3-phenylene, 2-phenyl-1,3-phenylene, 4-phenyl-1,3-phenylene, 5-phenyl-1,3-phenylene, 2-phenyl-1,4-phenylene, 2,6-pyridinediyl, 2,4-pyridinediyl, 3,5-pyridinediyl, 3,6-pyridinediyl, 5,8-quinolinediyl, 2,4-toluenediyl, 2,5-xylenediyl and so on. As isomers of the arylenes other than those at the 1,3- and 1,4-positions, which are not described above, there are, e.g., 2,4-quinolinediyl, 2,5-quinolinediyl, 2,6-quinolinediyl, and the like.
In other aspect of the present invention, there is provided a resin composition, e.g., a blend, comprising the polyarylene and a synthetic organic polymer. For example, there is provided a resin composition comprising 1 to 99 wt % of the polyarylene and 99 to 1 wt % of the synthetic organic polymer. There is also provided 10 to 90 wt %of the polyarylene and 90 to 10 wt % of the synthetic organic polymer.
The synthetic organic polymer includes a thermoplastic polymer, a thermosetting polymer, engineering plastics, etc. The synthetic organic polymer may also be a copolymer. Examples of the thermoplastic polymer are polyolefin such as polyethylene, polypropylene, polycycloolefin, ethylene-propylene copolymer, etc.; polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, polymethacrylic acid, polystyrene, polyamide, polyester, polycarbonate, etc. Examples of the thermosetting polymer are phenol resin, urea resin, melamine resin, alkyd resin, unsaturated polyester resin, epoxy resin, silicone resin and polyurethane resin. Examples of the engineering plastics include polyimide, polyphenylene oxide, polysulfone, etc. The synthetic organic polymer may be synthetic rubber such as styrene-butadiene, etc., or fluorine resin such as polytetrafluoroethylene, etc.
The resin composition may also contain a variety of additives. Examples of the additives are plasticizers, antistatic agents, coloring agents, etc. The resin composition may further contain reinforcing agents such as glass fibers, carbon fibers, etc.
The polyarylene or resin composition in accordance with the present invention can be prepared into the shape of fibers, films or sheets using methods publicly known to one skilled in the art. Examples of such methods include, but are not limited to, melt spinning, spinning from a solution, dry jet wet spinning, extrusion, flow casting and molding. The fibers, films or sheets are further processed by means of calender molding, embossing, forming or other means publicly known to one skilled in the art.
In a still further aspect of the present invention, there is provided a teraryl represented by formula (III) or (IV). In formula (III) or (IV), Ar1, Ar2, R1, R2, A1 and A2 have the same significance as defined above.
X1 and X2, which may be the same or different, each represents independently a leaving group. Examples of the leaving group are a halogen atom such as F, Cl, Br or I, p-toluenesulfonyl group, etc., with particular preference being Br.
In a still further aspect of the present invention, there is provided a process for producing the polyarylene represented by formula (I) or (II) described above. This reaction is shown by the following equation: 
(wherein Ar1, Ar2, R1, R2, A1, A2, X1 and X2 have the same significance as defined above); 
(wherein Ar1, Ar2, R1, R2, A1, A2, X1 and X2 have the same significance as defined above).
Polymerization is carried out by coupling monomers through removal of the leaving groups X1 and X2 with a reducing agent. As the reducing agent, e.g., metals from Groups I-XIV of the Periodic Table can be widely employed. Examples of the reducing agent include metals from Group I of the Periodic Table such as lithium or sodium; metals from Group II such as magnesium; metals from Group XI such as copper; and metals from Group XII such as zinc.
The polymers of the present invention can be formed by polymerization of monomers described above through reductive coupling using a nickel (0) compound described in T. Kanbara, T. Kushida, N. Saito, I. Kuwajima, K. Kubota and T. Yamamoto, Chemistry Letters, 1992, 583-586, or through nickel catalyst-reductive coupling described in U.S. Pat. Nos. 5,227,457 or 5,241,044.
That is, where a mild reducing agent such as magnesium or zinc is used, an organic metal complex catalyst such as bis(triphenylphosphine)dichloronickel or dichloro(2,2xe2x80x2-bipyridine)nickel, PdCl2(2,2xe2x80x2-bipyridine) may be employed, since polymerization proceeds under relatively mild conditions. Nitrogen-containing compounds such as bipyridine, or phosphorus-containing organic compounds such as phosphine may also be co-present as a co-catalyst.
As examples of the organic metal complex, those consisting of the central metal from Groups III-XI, preferably from Groups VI-XI of the Periodic Table, with ligands such as a phosphine; an aromatic amine such as pyridine or bipyridine, a halogen atom, etc. are preferably employed. Preferably, the central metal takes so-called tetra- to hexa-valent coordination and more preferably, is a metal from Group X of the Periodic Table. Examples of the phosphine include, but are not limited to, triphenylphosphine and methyldiphenylphosphine.
Polymerization using magnesium as a reducing agent is described in T. Yamamoto et al., Bull. Chem. Soc. Jpn., 1978, 51, 2091, T. Yamamoto, Prog. Polym. Sci., 1992, 17, 1155, and M. Rehahan et al., Polymer, 1989, 30, 1054.
Polymerization using zinc as a reducing agent is described in, e.g., T. Yamamoto et al., Makromol. Chem., 1989, 190, 1649, M. Ueda et al., Macromolecules, 1990, 23, 926, I. Colon et al., J. Polym. Sci., Polym. Chem. Ed., 1990, 28, 367, M. Ueda et al., J. Polym. Sci., Chem. Ed., 1992, 30, 1567, V. Chaturvede et al., and J. Chem. Soc., Chem. Commun., 1992, 1658.
The polymerization is carried out preferably at temperatures from xe2x88x9280xc2x0 C. to 300xc2x0 C., more preferably at 0xc2x0 C. to 150xc2x0 C. Pressure is applied in the range of 0.1 bar to 2500 bars, preferably 0.5 bar to 10 bars. The polymerization can be carried out continuously or batch-wise, in one step or in a multi-step, in a solution or a suspension, in a gaseous phase or in a supercritical medium.
As a solvent, an aliphatic or aromatic solvent can be used; preferably, a polar solvent is employed. Examples of the solvent are an ethereal solvent such as tetrahydrofuran or diethyl ether, a halogenated hydrocarbon such as methylene chloride, a halogenated aromatic hydrocarbon such as o-dichlorobenzene, an amide such as N,N-dimethylformamide, and a sulfoxide such as dimethylsulfoxide.
In a still further aspect of the present invention, there is provided a process for producing a teraryl represented by formula (IIIa) or (IVa) described above. This reaction is shown by the following equation: 
(wherein Ar1, Ar2, R1, R2, A12, A22, X1 and X2 have the same significance as defined above); 
(wherein Ar1, Ar2, R1, R2, A1a, A2a, X1 and X2 have the same significance as defined above);
The reaction is carried out preferably in the presence of a catalyst. As the catalyst there can be used metal compounds from Groups IV-XV of the Periodic Table, particularly metal compounds from Groups VIII-XV of the Periodic Table. For example, metal salts such as CuX, NiX2 or BiX3 (wherein X is a halogen atom such as chlorine or bromine atom) are employed. Alternatively, the organometallic complexes, especially a nickel complex, which are herein exemplified in the description on the polymerization may be employed.
The formation of a benzene ring by reacting a metallacyclopentadiene such as zirconacyclopentadiene with an acetylene derivative in the presence of CuCl is described in T. Takahashi et al., J. Am. Chem. Soc., 1998, 120, 1672-1680.
Where at least one of A1a and A2a is an electron-donating group such as an alkyloxycarbonyl group, an aryloxycarbonyl group, nitrile group, etc., a copper salt such as copper chloride is preferably used. On the other hand, where A1a and A2a are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, etc., a nickel complex is preferably used.
When of A1a and A2a is cyano group or an alkoxycarbonyl group, this substituent can be converted into carbamoyl group (xe2x80x94C(xe2x95x90O)NH2), a haloformyl group (xe2x80x94C(xe2x95x90O)xe2x80x94X, wherein X is a halogen atom) or formyl group (xe2x80x94C(xe2x95x90O)xe2x80x94H).
The reaction is carried out preferably at temperatures from xe2x88x9280xc2x0 C. to 300xc2x0 C., more preferably at xe2x88x9220xc2x0 C. to 50xc2x0 C. Pressure is applied in the range of 0.1 bar to 2500 bars, preferably 0.5 bar to 10 bars. The reaction is preferably carried out in situ without separating the metallacyclopentadiene shown by formula (V) or (VI) described above.
In a still further aspect of the present invention, the metallacyclopentadiene shown by formula (V) or (VI) described above is provided. The metallacyclopentadiene can be synthesized from a metallocene according to the following equation: 
(wherein Ar1, R1, A1, X1, L1 and L2have the same significance as defined above; B is a crosslinking group; and Z1 and Z2, which may be the same or different, each represents independently a ligand that can be split off);
xe2x80x83X1xe2x80x94Ar1xe2x80x94Cxe2x89xa1Cxe2x80x94Bxe2x80x94Cxe2x89xa1Cxe2x80x94Ar2xe2x80x94X2xe2x80x83xe2x80x83(VIIIb)

(wherein Ar1, Ar2, X1, X2, L1 and L2 have the same significance as defined above; B is a crosslinking group; and Z1 and Z2, which may be the same or different, each represents independently a ligand that can be split off); 
(wherein Ar1, Ar2, R1, R2, X1, X2, L1 and L2 have the same significance as defined above; and Z1 and Z2, which may be the same or different, each represents a ligand that can be split off).
B is a crosslinking group and hydrocarbon group, which may be intervened by, e.g., an oxygen atom, especially an alkylene group which may be intervened by an oxygen atom.
There is no restriction on Z1 and Z2, so long as they can be coordinated with M. Examples of Z1 and Z2 include a halogen atom, an olefin such as ethylene, an alkyl group, and the like.
The reaction described above is carried out preferably at xe2x88x92120xc2x0 C. to 50xc2x0 C., more preferably at xe2x88x92120xc2x0 C. to 0xc2x0 C., in the presence of a strong base such as an alkyl lithium. The formation of metallacyclopentadienes is described in, e.g., J. Am. Chem. Soc., 1994, 116, 1880-1889.
As M, metal complexes containing metals from Group IV or the lanthanide metal series of the Periodic Table are preferably employed. Metal complexes containing a non-localized cyclic xcex75-coordination type ligand are also preferred.
L1 and L2 are preferably a non-localized cyclic xcex75-coordination type ligand. Examples of the non-localized cyclic xcex75-coordination type ligand are unsubstituted cyclopentadienyl group and a substituted cyclopentadienyl group. Examples of the substituted cyclopentadienyl group include methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, t-butylcyclopentadienyl, dimethylcyclopentadienyl, diethylcyclopentadienyl, diisopropylcyclopentadienyl, di-t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, benzindenyl, fluorenyl, benzofluorenyl, tetrahydrofluorenyl and octahydrofluorenyl groups.
In the non-localized cyclic xcex75-coordination type ligand, one or more atoms of the non-localized cyclic xcex75-coordination type may be substituted for the hetero atom. The ligand may contain, in addition to hydrogen, one or more hetero atoms such as the elements from Group XIV and/or Groups XV, XVI and XVII, of the Periodic Table.
The non-localized cyclic xcex75-coordination type ligand, e.g., the cyclopentadienyl group may be crosslinked with the central metal by one or more crosslinking ligands that may be cyclic. Examples of the crosslinking ligands are CH2, CH2CH2, CH(CH3)CH2, CH(C4H9)C(CH3)2, C(CH3)2, (CH3)2Si, (CH3)2Ge, (CH3)2Sn, (C6H5)2Si, (C6H5)(CH3)Si, (C6H5)2Ge, (C6H5)2Sn, (CH2)4Si, CH2Si(CH3)2, o-C6H4 or 2,2xe2x80x2-(C6H4))2.
Two or more non-localized cyclic xcex75-coordination type ligands, e.g., the cyclopentadienyl groups may be crosslinked with each other by one or more crosslinking ligands that may be cyclic. Examples of the crosslinking ligands are CH2, CH2CH2, CH(CH3)CH2, CH(C4H9)C(CH3)2, C(CH3)2, (CH3)2Si, (CH3)2Ge, (CH3)2Sn, (C6H5)2Si, (C6H5)(CH3)Si, (C6H5)2Ge, (C6H5)2Sn, (CH2)4Si, CH2Si(CH3)2, o-C6H4 or 2,2xe2x80x2-(C6H4)2.
The metallacyclopentadienes of the present invention also embrace compounds containing two or more metallacyclopentadiene moieties. Such compounds are known as multinuclear metallocenes. The multinuclear metallocenes described above may have any substitution mode or any crosslinking mode. The independent metallocene moieties in the multinuclear metallocene may be the same or different. Examples of the multinuclear metallocenes are described in, e.g., EP-A-632063, Japanese Patent Unexamined Publication (Laid-open) Nos. 4-80214 and 4-85310 and EP-A-654476.
The metallacyclopentadienes of the present invention can be synthesized using, e.g., the metallocenes below.
In the case of dichloro-compounds such as
bis(indenyl)dichlorozirconium;
bis(fluorenyl)dichorozirconium;
(indenyl)(fluorenyl)dichlorozirconium;
bis(cyclopentadienyl)dichlorotitanium;
(dimethylsilanediyl)bis(indenyl)dichlorozirconium;
(dimethylsilanediyl)bis(tetrahydroindenyl)dichlorozirconium; (dimethylsilanediyl)(indenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-methylindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-ethylindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-methyl-4,5-benzindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-ethyl-4,5-benzindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-methyl-4-phenylindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-ethyl-4-phenylindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-methyl-4,6-diisopropylindenyl)dichlorozirconium; etc., the metallacyclopentadienes are formed either after reduction of these compounds with a strong base, e.g.,an alkali metal such as sodium, an alkaline earth metal such as magnesium, or after their conversion into the corresponding dialkyl compounds. Examples of the metallocens are:
bis(cyclopentadienyl)dibutylzirconium;
bis(indenyl)dibutylzirconium;
bis(fluorenyl)dibutylzirconium;
(indenyl)(fluorenyl)dibutylzirconium;
(3-methyl-5-naphthylindenyl)(2,7-di-tert-butylfluorenyl)dibutylzirconium;
(3-methyl-5-naphthylindenyl)(3,4,7-trimethoxyfluorenyl)dibutylzirconium;
(pentamethylcyclopentadienyl)(tetrahydroindenyl)dibutylzirconium;
(cyclopentadienyl)(1-octene-8-ylcyclopentadienyl)dibutyzirconium;
(indenyl)(1-butene-4-ylcyclopentadienyl)dibutylzirconium;
[1,3-bis(trimethylsilyl)cyclopentadienyl](3,4-benzofluorenyl)dibutylzirconium;
bis(cyclopentadienyl)dibutyltitanium;
dimethylsilanediylbis(indenyl)dibutylzirconium;
dimethylsilanediylbis(tetrahydroindenyl)dibutylzirconium;
dimethylsilanediyl(cyclopentadienyl)(indenyl)dibutylzirconium;
dimethylsilanediylbis(2-methylindenyl)dibutylzirconium;
dimethylsilanediylbis(2-ethylindenyl)dibutylzirconium;
dimethylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylzirconium;
dimethylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylzirconium;
dimethylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;
dimethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;
dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;
dimethylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylzirconium;
dimethylsilanediyl(2-ethylindenyl)(2-ethyl-4-phenylnaphthyl)dibutylzirconium;
dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylzirconium;
dimethylsilanediylbis(2-methyl-4-phenylindenyl)dibutylzirconium;
dimethylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylzirconium;
dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;
dimethylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;
dimethylsilanediylbis(2-methyl-4-naphthylindenyl)dibutyzirconium;
dimethylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutylzirconium;
methylphenylsilanediylbis(indenyl)dibutylzirconium;
methylphenylsilanediyl(cyclopentadienyl)(indenyl)dibutylzirconium;
methylphenylsilanediylbis(tetrahydroindenyl)dibutylzirconium;
methylphenylsilanediylbis(2-methylindenyl)dibutylzirconium;
methylphenylsilanediylbis(2-ethylindenyl)dibutylzirconium;
methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylzirconium;
methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylzirconium;
methylphenylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;
methylphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;
methylphenylsilanediyl(2-ethylindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;
methylphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl1-4-phenylindenyl)dibutylzirconium;
methylphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-indenyl)dibutylzirconium;
methylphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylzirconium;
methylphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutylzirconium;
methylphenylsilanediylbisdibutylzirconium;
methylphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;
methylphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;
methylphenylsilanediylbis(4-naphthylindenyl)dibutylzirconium;
methylphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutylzirconium;
diphenylsilanediylbis(indenyl)dibutylzirconium;
diphenylsilanediylbis(2-methylindenyl)dibutylzirconium;
diphenylsilanediylbis(2-ethylindenyl)dibutylzirconium;
diphenylsilanediyl(cyclopentadienyl)(indenyl)dibutylzirconium;
diphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylzirconium;
diphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylzirconium;
diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;
diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylzirconium;
diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylzirconium;
diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4-naphthylindenyl)dibutylzirconium;
diphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylzirconium;
diphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutylzirconium;
diphenylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylzirconium;
diphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;
diphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;
diphenylsilanediylbis(2-methyl-4-naphthylindenyl)dibutyzirconium;
diphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(indenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-methylindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-ethylindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-methyl-4,5-benzindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-ethyl-4,5-benzindenyl)dibutylzirconium;
1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)dibutylzirconium;
1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)dibutylzirconium;
1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-ethyl-4-phenylindenyl)dibutylzirconium;
1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-ethyl-4-naphthylindenyl)dibutylzirconium;
1-silacyclopentane-1-(2-methylindenyl)-1-(4-phenylindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-methyl-4-phenylindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-methyl-4-naphthylindenyl)dibutylzirconium;
1-silacyclopentane-1,1-bis(2-ethyl-4-naphthylindenyl)dibutylzirconium;
bis(cyclopentadienyl)dibutyltitanium;
ethylene-1,2-bis(indenyl)dibutylzirconium;
ethylene-1,2-bis(tetrahydroindenyl)dibutylzirconium;
ethylene-1-(cyclopentadienyl)-2-(1-indenyl)dibutylzirconium;
ethylene-1-(cyclopentadienyl)-2-(2-indenyl)dibutylzirconium;
ethylene-1-(cyclopentadienyl)-2-(2-methyl-1-indenyl)dibutylzirconium;
ethylene-1,2-bis(2-methylindenyl)dibutylzirconium;
ethylene-1,2-bis(2-ethylindenyl)dibutylzirconium;
ethylene-1,2-bis(2-methyl-4,5-benzindenyl)dibutylzirconium;
ethylene-1,2-bis(2-ethyl-4,5-benzindenyl)dibutylzirconium;
ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;
ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;
ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;
ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)dibutylzirconium;
ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutylzirconium;
ethylene-1-(2-methylindenyl)-2-(4-phenylindenyl)dibutylzirconium;
ethylene-1,2-bis(2-methyl-4-phenylindenyl)dibutylzirconium;
ethylene-1,2-bis(2-ethyl-4-phenylindenyl)dibutylzirconium;
ethylene-1,2-bis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;
ethylene-1,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;
ethylene-1,2-bis(2-methyl-4-naphthylindenyl)dibutylzirconium;
ethylene-1,2-bis(2-ethyl-4-naphthylindenyl)dibutylzirconium;
propylene-2,2-bis(indenyl)dibutylzirconium;
propylene-2-cyclopentadienyl-2-(1-indenyl)dibutylzirconium;
propylene-2-cyclopentadienyl-2-(4-phenyl-1-indenyl)dibutylzirconium;
propylene-2-cyclopentadienyl-2-(9-fluorenyl)dibutylzirconium;
propylene-2-cyclopentadienyl-2-(2,7-dimethoxy-9-fluorenyl)dibutylzirconium;
propylene-2-cyclopentadienyl-2-(2,7-di-tert-butyl-9-fluorenyl)dibutylzirconium;
propylene-2-cyclopentadienyl-2-(2,7-dibromo-9-fluorenyl)dibutylzirconium;
propylene-2-cyclopentadienyl-2-(2,7-diphenyl-9-fluoreny]dibutylzirconium;
propylene-2-cyclopentadienyl-2-(2,7-dimethyl-9-fluorenyl)dibutylzirconium;
propylene-2-(3-methylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutylzirconium;
propylene-2-(3-tert-butylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutylzirconium;
propylene-2-(3-trimethylsilylcyclopentadienyl)-2-(3,6-di-tert-butyl-9-fluorenyl)dibutylzirconium;
propylene-2-cyclopentadienyl-2-[2,7-bis(3-butene-1-yl)-9-fluorenyl]dibutylzirconium;
propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluorenyl)dibutylzirconium;
propylene-2,2-bis(tetrahydroindenyl)dibutylzirconium;
propylene-2,2-bis(2-methylindenyl)dibutylzirconium;
propylene-2,2-bis(2-ethylindenyl)dibutylzirconium;
propylene-2,2-bis(2-methyl-4,5-benzindenyl)dibutylzirconium;
propylene-2,2-bis(2-ethyl-4,5-benzindenyl)dibutylzirconium;
propylene-2,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylzirconium;
propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;
propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylzirconium;
propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)dibutylzirconium;
propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutylzirconium;
propylene-2-(2-methylindenyl)-2-(4-phenylindenyl)dibutyzirconium;
propylene-2,2-bis(2-methyl-4-phenylindenyl)dibutylzirconium;
propylene-2,2-bis(2-ethyl-4-phenylindenyl)dibutylzirconpropylene-2,2-bis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium;
propylene-2,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutylzirconium;
propylene-2,2-bis(2-methyl-4-naphthylindenyl)dibutylzirconium;
propylene-2,2-bis(2-ethyl-4-naphthylindenyl)dibutylzirconium;
1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylzirconium]hexane;
1,6-bis[methylsilylbis(2-methyl-4,5-benzindenyl)dibutylzirconium]hexane;
1,6-bis[methylsilylbis(2-ethyl-4-phenylindenyl)dibutylzirconium]hexane;
1,6-bis[methylsilylbis(2-methyl-4-naphthylindenyl)dibutylzirconium]hexane;
1,6-bis[methylsilylbis(2-methyl-4,6-diisopropylindenyl)dibutylzirconium]hexane;
1,6-bis[methylsilyl(2-methyl-4-phenylindenyl)(4,5-benzindenyl)dibutylzirconium]hexane;
1-[methylsilylbis(tetrahydroindenyl)dibutylzirconium]-6-[ethylstannyl(cyclopentadienyl)(fluorenyl)dibutylzirconium]hexane;
1,6-disila-1,1,6,6-tetramethyl-1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylzirconium]hexane;
1,4-disila-1,4-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylzirconium]cyclohexane;
[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(pentamethylcyclopentadienyldibutylzirconium);
[1,4-bis(9-fluorenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutylzirconium);
[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutylzirconium);
[1-(1-indenyl)-6-(2-phenyl-1-indenyl)-1,1,6,6-tetraethyl-1,6-disila-4-oxahexane]bis(tert-butylcyclopentadienyldibutylzirconium);
[1,10-bis(2,3-dimethyl-1-indenyl)-1,1,10,10-tetramethyl-1,10-digermadecane]bis(2-methyl-4-phenylindenyldibutylzirconium);
(1-methyl-3-tert-butylcyclopentadienyl)(1-phenyl-4-methoxy-7-chlorofluorenyl)dibutylzirconium;
(4,7-dichloroindenyl)(3,6-dimesitylfluorenyl)dibutylzirconium;
bis(2,7-di-tert-butyl-9-cyclohexylfluorenyl)dibutylzirconium;
(2,7-dimethylfluorenyl)[2,7-bis(1-naphthyl)fluorenyl]dibutylzirconium;
dimethylsilylbis(fluorenyl)dibutylzirconium;
dibutylstannylbis(2-methylfluorenyl)dibutylzirconium;
1,1,2,2-tetraethyldisilanediyl(2-methylindenyl)(4-phenylfluorenyl)dibutylzirconium;
propylene-1-(2-indenyl)-2-(9-fluorenyl)dibutylzirconium;
1,1-dimethyl-1-silaethylenebis(fluorenyl)dibutylzirconium;
[4-(cyclopentadienyl)4,7,7-trimethyl(tetrahydroindenyl)dibutylzirconium;
[4-(cyclopentadienyl)-4,7-dimethyl-7-phenyl(5,6-dimethyl]tetrahydroindenyl]dibutylzirconium;
[4-(cyclopentadienyl)-4,7-dimethyl-7-(1-naphthyl)(7-phenyltetrahydroindenyl)]dibutylzirconium;
[4-(cyclopentadienyl)-4,7-dimethyl-7-butyl(6,6-diethyltetrahydroindenyl)]dibutylzirconium;
[4-(3-tert-butylcyclopentadienyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutylzirconium;
[4-(1-indenyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutylzirconium;
bis(cyclopentadienyl)dibutylhafnium;
bis(indenyl)dibutylvanadium;
bis(fluorenyl)dibutylscandium;
(indenyl)(fluorenyl)dibutylniobium;
(2-methyl-7-naphthylindenyl)(2,6-di-tert-butylfluorenyl)dibutyltitanium;
(pentamethylcyclopentadienyl)(tetrahydroindenyl)butylhafnium bromide;
(cyclopentadienyl)(1-octene-8-ylcyclopentadienyl)dibutylhafnium;
(indenyl)(2-butene-4-ylcyclopentadienyl)dibutyltitanium;
[1,3-bis(trimethylsilyl)cyclopentadienyl](3,4-penzofluorenyl)dibutylniobium;
bis(cyclopentadienyl)dibutyltitanium;
dimethylsilanediylbis(indenyl)dibutyltitanium;
dimethylsilanediylbis(tetrahydroindenyl)dibutylhafnium;
dimethylsilanediyl(cyclopentadienyl)(indenyl)dibutyltitanium;
dimethylsilanediylbis(2-methylindenyl)dibutylhafnium;
dimethylsilanediylbis(2-ethylindenyl)methylscandium;
dimethylsilanediylbis(2-butyl-4,5-benzindenyl)dibutylniobium;
dimethylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutyltitanium;
dimethylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutyltitanium;
dimethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutyltitanium;
dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutylhafnium;
dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)methylscandium;
dimethylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4-naphthylindenyl)dibutyltitanium;
dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutylhafnium;
dimethylsilanediylbis(2-methyl-4-phenylindenyl)dibutylniobium;
dimethylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylvanadium;
dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium;
dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylvanadium;
dimethylsilanediylbis(2-methyl-4-naphthylindenyl)butylhafnium bromide;
dimethylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutyltitanium;
methylphenylsilanediylbis(indenyl)dibutyltitanium;
methylphenylsilanediyl(cyclopentadienyl)(indenyl)hafnium;
methylphenylsilanediylbis(tetrahydroindenyl)dibutylhafnium;
methylphenylsilanediylbis(2-methylindenyl)dibutyltitanium;
methylphenylsilanediylbis(2-ethylindenyl)dibutylhafnium;
methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutylhafnium;
methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylvanadium;
methylphenylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutyltitanium;
methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)butyltitanium bromide;
methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)dibutyltitanium;
methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylhafnium;
methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)(2-ethyl-4-phenylindenyl)dibutylhafnium;
methylphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutyltitanium;
methylphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutylhafnium;
methylphenylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylvanadium;
methylphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutyltitanium;
methylphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylhafnium;
methylphenylsilanediylbis(2-methyl-4-naphthylindenyl)dibutylhafnium;
methylphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutyltitanium;
diphenylsilanediylbis(indenyl)dibutyltitanium;
diphenylsilanediylbis(2-methylindenyl)dibutylhafnium;
diphenylsilanediylbis(2-ethylindenyl)dibutyltitanium;
diphenylsilanediylbis(cyclopentadienyl)(indenyl)dibutylhafnium;
diphenylsilanediylbis(2-methyl-4,5-benzindenyl)dibutyltitanium;
diphenylsilanediylbis(2-ethyl-4,5-benzindenyl)dibutylhafnium;
diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4,5-phenylindenyl)dibutylhafnium;
diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-methyl-4,5-phenylindenyl)dibutyltitanium;
diphenylsilanediyl(2-methyl-4,5-benzindenyl)(2-ethyl-4,5-phenylindenyl)dibutylhafnium;
diphenylsilanediyl(2-ethyl-4,5-benzindenyl)(2-ethyl-4,5-phenylindenyl)dibutyltitanium;
diphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dibutyltitanium;
diphenylsilanediylbis(2-methyl-4-phenylindenyl)dibutyltitanium;
diphenylsilanediylbis(2-ethyl-4-phenylindenyl)dibutylhafnium;
diphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium;
diphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dibutylhafnium;
diphenylsilanediylbis(2-methyl-4-naphthylindenyl)dibutylhafnium;
diphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dibutyltitanium;
1-silacyclopentane-1,1-bis(indenyl)dibutylhafnium;
1-silacyclopentane-1,1-bis(2-methylindenyl)dibutylhafnium;
1-silacyclopentane-1,1-bis(2-ethylindenyl)dibutylhafnium;
1-silacyclopentane-1,1-bis(2-methyl-4,5-benzindenyl)dibutyltitanium;
1-silacyclopentane-1,1-bis(2-ethyl-4,5-benzindenyl)dibutylhafnium;
1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)methylscandium;
1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-methyl-4-phenylindenyl)dibutylhafnium;
1-silacyclopentane-1-(2-methyl-4,5-benzindenyl)-1-(2-ethyl-4-phenylindenyl)dibutyltitanium;
1-silacyclopentane-1-(2-ethyl-4,5-benzindenyl)-1-(2-ethyl-4-phenylindenyl)dibutylhafnium;
1-silacyclopentane-1-(2-methylindenyl)-1-(4-phenylindenyl)dibutylhafnium;
1-silacyclopentane-1,1-bis(2-methyl-4-phenylindenyl)dibutylhafnium;
1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindenyl)dibutyltitanium bromide;
1-silacyclopentane-1,1-bis(2-methyl-4,6-diisopropylindenyl)dibutyltitanium;
1-silacyclopentane-1,1-bis(2-ethyl-4,6-diisopropylindenyl)dibutyltitanium;
1-silacyclopentane-1,1-bis(2-methyl-4-naphthylindenyl)methylscandium;
1-silacyclopentane-1,1-bis(2-ethyl-4-naphthylindenyl)dibutylhafnium;
bis(cyclopentadienyl)dibutyltitanium;
ethylene-1,2-bis(indenyl)methylscandium;
ethylene-1,2-bis(tetrahydroindenyl)dibutyltitanium;
ethylene-1-(cyclopentadienyl)-2-(1-indenyl)dibutylhafnium;
ethylene-1-(cyclopentadienyl)-2-(2-indenyl)butyltitanium bromide;
ethylene-1-(cyclopentadienyl)-2-(2-methyl-1-indenyl)dibutylhafnium;
ethylene-1,2-bis(2-methylindenyl)dibutylhafnium;
ethylene-1,2-bis(2-ethylindenyl)dibutylhafnium;
ethylene-1,2-bis(2-methyl-4,5-benzindenyl)dibutylhafnium;
ethylene-1,2-bis(2-ethyl-4,5-benzindenyl)dibutyltitanium;
ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutyltitanium;
ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutyltitanium;
ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutyltitanium;
ethylene-1-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)methylscandium;
ethylene-1-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutylhafnium;
ethylene-1-(2-methylindenyl)-2-(4-phenylindenyl)dibutyltitanium;
ethylene-1,2-bis(2-methyl-4-phenylindenyl)dibutylhafnium;
ethylene-1,2-bis(2-ethyl-4-phenylindenyl)dibutylhafnium;
ethylene-1,2-bis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium;
ethylene-1,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutyltitanium;
ethylene-1,2-bis(2-methyl-4-naphthylindenyl)dibutyltitanium;
ethylene-1,2-bis(2-ethyl-4-naphthylindenyl)dibutylhafnium;
propylene-2,2-bis(indenyl)dibutylhafnium;
propylene-2-cyclopentadienyl-2-(1-indenyl)dibutyltitanium;
propylene-2-cyclopentadienyl-2-(4-phenyl-1-indenyl)dibutyltitanium;
propylene-2-cyclopentadienyl-2-(9-fluorenyl)dibutylhafnium;
propylene-2-cyclopentadienyl-2-(2,7-dimethoxy-9-fluorenyl)dibutylhafnium;
propylene-2-cyclopentadienyl-2-(2,7-di-tert-butyl-9-fluorenyl)dibutylhafnium;
propylene-2-cyclopentadienyl-2-(2,7-dibromo-9-fluorenyl)dibutyltitanium;
propylene-2-cyclopentadienyl-2-(2,7-diphenyl-9-fluorenyl)dibutylhafnium;
propylene-2-cyclopentadienyl-2-(2,7-dimethyl-9-fluorenyl)dibutyltitanium;
propylene-2-(3-methylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutylhafnium;
propylene-2-(3-tert-butylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dibutyltitanium;
propylene-2-(3-trimethylsilylcyclopentadienyl)-2-(3,6-di-tert-butyl-9-fluorenyl)dibutyltitanium;
propylene-2-cyclopentadienyl-2-[2,7-bis(3-butene-1-yl)-9-fluorenyl]dibutylhafnium;
propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluoreny-1)dibutyltitanium;
propylene-2,2-bis(tetrahydroindenyl)dibutylhafnium;
propylene-2,2-bis(2-methylindenyl)dibutylhafnium;
propylene-2,2-bis(2-ethylindenyl)dibutyltitanium;
propylene-2,2-bis(2-methyl-4,5-benzindenyl)dibutyltitanium;
propylene-2,2-bis(2-ethyl-4,5-benzindenyl)dibutylhafnium;
propylene-2,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylene-7-ylidene)dibutylhafnium;
propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutylhafnium;
propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-methyl-4-phenylindenyl)dibutyltitanium;
propylene-2-(2-methyl-4,5-benzindenyl)-2-(2-ethyl-4-phenylindenyl)dibutylhafnium;
propylene-2-(2-ethyl-4,5-benzindenyl)-2-(2-ethyl-4-naphthylindenyl)dibutyltitanium;
propylene-2-(2-methylindenyl)-2-(4-phenylindenyl)dibutylhafnium;
propylene-2,2-bis(2-methyl-4-phenylindenyl)dibutyltitanium;
propylene-2,2-bis(2-ethyl-4-phenylindenyl)dibutylhafnium;
propylene-2,2-bis(2-methyl-4,6-diisopropylindenyl)dibutyltitanium;
propylene-2,2-bis(2-ethyl-4,6-diisopropylindenyl)dibutylhafnium;
propylene-2,2-bis(2-methyl-4-naphthylindenyl)dibutyltitanium;
propylene-2,2-bis(2-ethyl-4-naphthylindenyl)dibutyltitanium;
1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylhafnium]hexane;
1,6-bis[methylsilylbis(2-methyl-4,5-benzindenyl)dibutyltitanium]hexane;
1,6-bis[methylsilylbis(2-ethyl-4-phenylindenyl)dibutylhafnium]hexane;
1,6-bis[methylsilylbis(2-methyl-4-naphthylindenyl)dibutyltitanium]hexane;
1,6-bis[methylsilylbis(2-methyl-4,6-diisopropylindenyl)dibutylhafnium]hexane; 1,6-bis[methylsilyl(2-methyl-4-phenylindenyl)(4,5-benzindenyl)dibutyltitanium]hexane;
1-[methylsilylbis(tetrahydroindenyl)dibutylhafnium]-6-[ethylstannyl(cyclopentadienyl)(fluorenyl)dibutyltitanium]hexane;
1,6-disila-1,1,6,6-tetramethyl-1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylhafnium]hexane;
1,4-disila-1,4-bis[methylsilylbis(2-methyl-4-phenylindenyl)dibutylhafnium]cyclohexane;
[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(pentamethylcyclopentadienyldibutylhafnium);
[1,4-bis(9-fluorenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutylhafnium);
[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldibutyltitanium);
[1-(1-indenyl)-6-(2-phenyl-1-indenyl)-1,1,6,6-tetraethyl-1,6-disila-4-oxahexane]bis(tert-butylcyclopentadienyldibutyltitanium);
[1,10-bis(2,3-dimethyl-1-indenyl)-1,1,10,10-tetramethyl-1,10-digermadecane]bis(2-methyl-4-phenylindenyldibutylhafnium);
(1-methyl-3-tert-butylcyclopentadienyl)(1-phenyl-4-methoxy-7-chlorofluorenyl)dibutyltitanium;
(4,7-dichloroindenyl)(3,6-dimesitylfluorenyl)dibutyltitanium;
bis(2,7-di-tert-butyl-9-cyclohexylfluorenyl)dibutylhafnium;
(2,7-dimesitylfluorenyl)[2,7-bis(1-naphthyl)fluorenyl]dibutylhafnium;
dimethylsilylbis(fluorenyl)dibutyltitanium;
dibutylstannylbis(2-methylfluorenyl)dibutylhafnium;
1,1,2,2-tetraethyldisilanediyl(2-methylindenyl)(4-phenylfluorenyl)dibutyltitanium;
propylene-1-(2-indenyl)-2-(9-fluorenyl)dibutylhafnium;
1,1-dimethyl-1-silaethylenebis(fluorenyl)dibutyltitanium;
[4-(cyclopentadienyl)4,7,7-trimethyl(tetrahydroindenyl]dibutyltitanium;
[4-(cyclopentadienyl)4,7-dimethyl-7-phenyl(5,6-dimethyltetrahydroindenyl]dibutylhafnium;
[4-(cyclopentadienyl)-4,7-dimethyl-7-(1-naphthyl)(7-phenyltetrahydroindenyl]dibutyltitanium;
[4-(cyclopentadienyl)-4,7-dimethyl-7-butyl(6.6-diethyltetrahydroindenyl)]dibutylhafnium;
[4-(3-tert-butylcyclopentadienyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutylhafnium;
[4-(1-indenyl)-4,7,7-trimethyl(tetrahydroindenyl)]dibutyltitanium;
bis(cyclopentadienyl)dibutylhafnium;
bis(cyclopentadienyl)dichlorozirconium;
bis(indenyl)dichlorozirconium;
bis(fluorenyl)dichlorozirconium;
(indenyl)(fluorenyl)dichlorozirconium;
bis(cyclopentadienyl)dichlorotitanium;
(dimethylsilanediyl)bis(indenyl)dichlorozirconium;
(dimethylsilanediyl)bis(tetrahydroindenyl)dichlorozirconium;
(dimethylsilanediyl)(indenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-methylindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-ethylindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-methyl-4,5-benzindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-ethyl-4,5-benzindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-methyl-4-phenylindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-ethyl-4-phenylindenyl)dichlorozirconium;
(dimethylsilanediyl)bis(2-methyl-4,6-diisopropylindenyl)dichlorozirconium;
bis(cyclopentadienyl)(xcex74-butadiene)zirconium;
bis(methylcyclopentadienyl)(xcex74-butadiene)zirconium;
bis(n-butylcyclopentadienyl)(xcex74-butadiene)zirconium;
bisindenyl(xcex74-butadiene)zirconium;
(tert-butylamido)dimethyl(tetramethyl-xcex75-cyclopentadienyl)silane(xcex74-butadiene)zirconium;
bis(2-methylbenzindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-indenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbisindenyl(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-indenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(xcex74-butadiene)zirconium;
isopropylidene(cyclopentadienyl)(fluorenyl)(xcex74-butadiene)zirconium;
isopropylidene(cyclopentadienyl)(indenyl)(xcex74-butadiene)zirconium;
(4-xcex75-cyclopentadienyl)-4,7,7-trimethyl-(xcex75,4,5,6,7-tetrahydroindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-indenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbisindenyl(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methylbenzindenyl)(xcex74-butadienezirconium;
dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-indenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbisindenyl(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methylbenzindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylbenzindenyl)(2-methylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-benzindenyl)(4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbisindenyl(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methylbenzindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylbenzindenyl)(2-methylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylbenzindenyl)(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(2-methylbenzindenyl)(4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(xcex74-butadiene)zirconium;
methylphenylmethylene(fluorenyl)(cyclopentadienyl)(xcex74-butadiene)zirconium;
diphenylmethylene(fluorenyl)(cyclopentadienyl)(xcex74-butadiene)zirconium;
isopropylidene(3-methylcyclopentadienyl)(fluorenyl)(xcex74-butadiene)zirconium;
dimethylsilanediyl(3-tert-butylcyclopentadienyl)(fluorenyl)(xcex74-butadiene)zirconium;
diphenylsilanediyl(3-(trimethylsilyl)cyclopentadienyl)(fluorenyl)(xcex74-butadiene)zirconium;
phenylmethylsilanediylbis(2-methylindenyl)(xcex74-butadiene)zirconium;
phenylmethylsilanediylbisindenyl(xcex74-butadiene)zirconium;
phenylmethylsilanediylbis(2-methyl-4,5-benzindenyl)(xcex74-butadiene)zirconium;
phenylmethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methylindenyl)(xcex74-butadiene)zirconium;
phenylmethylsilanediyl(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium; phenylmethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(xcex74-butadiene)zirconium;
phenylmethylsilanediylbis(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
phenylmethylsilanediylbis(2-ethyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
phenylmethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(xcex74-butadiene)zirconium;
phenylmethylsilanediylbis(2-methyl-4-naphthylindenyl)(xcex74-butadiene)zirconium;
ethylenebis(2-methylindenyl)(xcex74-butadiene)zirconium;
ethylenebisindenyl(xcex74-butadiene)zirconium;
ethylenebis(2-methyl-4,5-benzindenyl)(xcex74-butadiene)zirconium;
ethylene(2-methyl-4,5-benzindenyl)(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
ethylene(2-methylindenyl)(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
ethylene(2-methylindenyl)(4-phenyl-indenyl)(xcex74-butadiene)zirconium;
ethylenebis(2-methyl-4,5-benzindenyl)(xcex74-butadiene)zirconium;
ethylenebis(2-methyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
ethylenebis(2-methyl-4,6-diisopropylindenyl)(xcex74-butadiene)zirconium;
ethylenebis(2-methyl-4-naphthylindenyl)(xcex74-butadiene)zirconium;
ethylenebis(2-ethyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
ethylenebis(2-ethyl-4,6-diisopropylindenyl)(xcex74-butadiene)zirconium;
ethylenebis(2-ethyl-4-naphthylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2-ethyl-4-phenylindenyl)(xcex74-butadiene)zirconium;
dimethylsilanediylbis(2,3,5-trimethylcyclopentadienyl)(xcex74-butadiene)zirconium;
1,6-{bis[methylsilylbis(2-methyl-4-phenylindenyl(xcex74-butadiene)zirconium]}hexane;
1,6-{bis[methylsilylbis(2-ethyl-4-phenylindenyl(xcex74-butadiene)zirconium]}hexane;
1,6-{bis[methylsilylbis(2-methyl-4-naphthylindenyl(xcex74-butadiene)zirconium]}hexane;
1,6-{bis[methylsilylbis(2-methyl-4,5-benzindenyl(xcex74-butadiene)zirconium]}hexane;
1,6-{bis[methylsilyl(2-methyl-4-phenylindenyl)(2-methylindenyl(xcex74-butadiene)zirconium]}hexane;
1,2-{bis[methylsilylbis(2-methyl-4-phenylindenyl(xcex74-butadiene)zirconium]}ethane;
1,2-{bis[methylsilylbis(2-ethyl-4-phenylindenyl(xcex74-butadiene)zirconium]}ethane;
1,2-{bis[methylsilylbis(2-methyl-4-naphthylindenyl(xcex74-butadiene)zirconium]}ethane;
1,2-{bis[methylsilylbis(2-methyl-4,5-benzindenyl(xcex74-butadiene)zirconium)]}ethane; and,
1,2-{bis[methylsilyl(2-methyl-4-phenylindenyl)(2-methylindenyl)(xcex74-butadiene)zirconium]}ethane.